2 Ambient Air Pollution 1 An Introduction to Air Pollution 2

Gas

Symbol
Percent by volume
(Current
Atmosphere)
ppm
(Natural
Atmosphere)
ppm
(Current
Atmosphere)
Nitrogen
N
2
78.1

Oxygen
O
2
20.9

Argon Ar 0.92

Neon Ne

18.2

Helium He

5.2

Krypton Kr

1.14

Xenon Xe

0.09

Carbon
dioxide

CO


280.0
3
Methane
CH
4


0.750 1.77
4

Nitrous
oxide

N
2
O


0.270 0.318
5

Water
Vapor

H O
Variable
(0.004 to 4)




























2
370.0







2


Defining air pollution is not simple. One could claim that air pollution started
when humans began burning fuels. In other words, all man-made (anthropogenic)
emissions into the air can be called air pollution, because they alter the chemical
composition of the natural atmosphere. The increase in the global concentrations
of greenhouse gases CO
2
, CH
4
,
and N
2
O (shown in Table 1), can be called air
pollution using this approach, even though the concentrations have not found to be
toxic for humans and the ecosystem. One can refine this approach and only
consider anthropogenic emissions of harmful chemicals as air pollution.

However, this refined approach has some drawbacks. Firstly, one has to define
what harmful means. Harmful could mean an adverse effect on the health of
living things, an adverse effect on anthropogenic or natural non-living structures, or
a reduction in the airs visibility. Also, a chemical that does not cause any
short-term harmful effects may accumulate in the atmosphere and create a
long-term harmful effect.

For example, anthropogenic emissions of chlorofluorocarbons (CFCs) were once
considered safe because they are inert in the lowest part of the atmosphere called


2
Builtjes, P. (2003) The Problem Air Pollution. Chapter 1 of AIR QUALITY MODELING
Theories, Methodologies, Computational Techniques, and Available Databases and Software. Vol
I Fundamentals (P. Zannetti, Editor). EnviroComp Institute (http://www.envirocomp.org/) and
Air & Waste Management Association (http://www.awma.org/).
3
http://lwf.ncdc.noaa.gov/oa/climate/gases.html#cd
3 Ambient Air Pollution 1 An Introduction to Air Pollution 3


4
http://lwf.ncdc.noaa.gov/oa/climate/gases.html#m
5
http://lwf.ncdc.noaa.gov/oa/climate/gases.html#n2o
4 Ambient Air Pollution 1 An Introduction to Air Pollution 4


4


the troposphere. However, once these chemicals enter the stratosphere, ultraviolet
radiation can convert them into highly reactive species that can have a devastating
effect on stratospheric ozone. Similarly, anthropogenic CO
2
emissions from
combustion processes were considered safe because they are not toxic, but the
long-term accumulation of CO
2
in the atmosphere may lead to a climate change,
which could then be harmful to humans and the ecosystem.

Another drawback of this approach is that it does not consider natural emissions as
air pollution even though they can be very harmful, such as gases and particles from
volcanic eruptions, and smoke from forest fires caused by natural processes
(lightning strikes).

So besides anthropogenic emissions, it is useful to also consider geogenic
emissions and biogenic emissions as contributors to air pollution. Geogenic
6
emissions are defined as emissions caused by the non-living world, such as
volcanic emissions, sea-salt emissions, and natural fires. Biogenic emissions come
from the living world; such as volatile organic compound (VOC) emissions from
forests and CH emissions from swamps
7
.


Human activity can also influence geogenic and biogenic emissions. For example,
human applications of nitrogen fertilizers in agriculture can result in increased
biogenic emissions of nitrogen compounds from the soil. Also, humans can affect
the biogenic emissions of VOC by cutting down trees or planting trees. Lastly,
geogenic emissions of dust from the earths surface can be altered if the surface is
changed by human activity.

So taking all of the above into account, we can define an air pollutant as any
substance emitted into the air from an anthropogenic, biogenic, or geogenic source,
that is either not part of the natural atmosphere or is present in higher
concentrations than the natural atmosphere, and may cause a short-term or
long-term adverse effect.



2 Primary and Secondary Pollutants

Pollutants can be classified as primary or secondary. Primary pollutants are
substances that are directly emitted into the atmosphere from sources. The main
primary pollutants known to cause harm in high enough concentrations are the
following:
Carbon compounds, such as CO, CO
2
, CH
4
, and VOCs
Nitrogen compounds, such as NO, N
2
O, and NH
3

Sulfur compounds, such as H
2
S and SO
2



6
http://www.eionet.europa.eu/gemet/concept?langcode=en&cp=3640
7
Builtjes, P. (2003) see previous footnote.
5 Ambient Air Pollution 1 An Introduction to Air Pollution 5




Halogen compounds, such as chlorides, fluorides, and bromides
Particulate Matter (PM or aerosols), either in solid or liquid form, which
is usually categorized into these groups based on the aerodynamic diameter
of the particles
8,9
:
1. Particles less than 100 microns, which are also called inhalable
10

since they can easily enter the nose and mouth.
2. Particles less than 10 microns (PM
10
, often labeled fine in Europe).
These particles are also called thoracic since they can penetrate deep
in the respiratory system.
11

3. Particles less than 4 microns. These particles are often called
respirable
12
because they are small enough to pass completely
through the respiratory system and enter the bloodstream.
4. Particles less than 2.5 microns (PM
2.5
, labeled fine in the US).
5. Particles less than 0.1 microns (PM
0.1
, ultrafine).

Sulfur compounds were responsible for the traditional wintertime sulfur smog in
London in the mid 20
th
century. These anthropogenic pollutants have sometimes
reached lethal concentrations in the atmosphere, such as during the infamous
London episode of December 1952
13
.

Secondary pollutants are not directly emitted from sources, but instead form in the
atmosphere from primary pollutants (also called precursors). The main
secondary pollutants known to cause harm in high enough concentrations are the
following:
NO
2
and HNO
3
formed from NO
Ozone (O
3
) formed from photochemical reactions of nitrogen oxides and
VOCs
Sulfuric acid droplets formed from SO
2
,
and nitric acid droplets formed
from NO
2

Sulfates and nitrates aerosols (e.g., ammonium (bi)sulfate and ammonium
nitrate) formed from reactions of sulfuric acid droplets and nitric acid
droplets with NH
3
, respectively
Organic aerosols formed from VOCs in gas-to-particle reactions

In the 20
th
century, it was recognized that petroleum products are responsible for a
new type of smog, a photochemical summertime smog composed of secondary


8
http://www.aiha.org/abs05/po105.htm
9
http://www.greenfacts.org/glossary/pqrs/PM10-PM2.5-PM0.1.htm
10
Inhalable particles are also defined, especially in the US, as particles of 15 micrometers or less in
diameter:
http://iaspub.epa.gov/trs/trs_proc_qry.navigate_term?p_term_id=28097&p_term_cd=TERM .
11
PM10 particles are often defined as respirable, especially in the US:
http://www.epa.gov/eogapti1/module3/category/category.htm .
12
http://www.aiha.org/abs05/po105.htm
13
http://www.metoffice.com/education/secondary/students/smog.html
6 Ambient Air Pollution 1 An Introduction to Air Pollution 6




pollutants such as ozone, that is quite different from the winter sulfur smog
described earlier. This smog has been labeled Los Angeles smog, to differentiate
from the London smog described before.

Photochemical smog
14
was first recognized
15
in the city of Los Angeles in the
1940s. After decades of research, the smog was identified as the product of
photochemical reactions involving precursors (nitrogen oxides and VOC) and
sunlight, with the production of ozone and other secondary chemicals.

While nitrogen oxides are emitted by a wide variety of sources, automobiles mostly
emit VOCs, even though contributions can be found from vegetation and common
human activities, such as bakeries
16
.

Some secondary pollutants sulfates, nitrates, and organic particles can be
transported over large distances, such as hundreds and even thousands of miles.
Wet and dry deposition of these pollutants contributes to the acid deposition
problem
17
(often called acid rain), with possible damage to soils, vegetation, and
susceptible lakes.



3 Air Pollution Regulation

In the last few decades, especially after the milestone 1970 Clean Air Act in the US,
air pollution has been regulated all over the world through a series of laws and
regulations.

The European commission has developed a series of framework directives for
controlling ambient air pollution and monitoring concentrations. Daughter
directives have followed that give thresholds, define the reporting requirements,
and specify the monitoring methods and number of observations for SO
2
, NO
2
,
particulate matter (PM), lead, and tropospheric (low-level) ozone (O
3
)
18
. More
information can be found at: http://europe.eu.int/comm/environment/air/ambient.htm.

The United Nations Economic Commission for Europe (UN-ECE) has created
protocols to reduce long-range transboundary air pollution. More information can
be found at: http://www.emep.int.





14
http://www.epa.qld.gov.au/environmental_management/air/air_quality_monitoring/air_pollutant
s/ozone/
15
http://www.pbs.org/now/science/smog.html
16
The by-products of fermenting yeast are CO

2
and ethanol (a VOC). So baking bread in large
quantities can contribute to ozone formation due to emissions of VOCs.
17
http://en.wikipedia.org/wiki/Acid_rain
18
Ambient ozone, a pollutant, is often defined as tropospheric to differentiate from stratospheric
ozone, which is a beneficial chemical.
7 Ambient Air Pollution 1 An Introduction to Air Pollution 7




New developments in air pollution modeling, research, and regulations in Europe
are listed at the EUROTRAC-project
19
.

In the United States, the Environmental Protection Agency (US-EPA) has
established air quality standards to protect public health, including the health of
sensitive populations such as children, older adults, and people with asthma.
US-EPA also sets limits to protect public welfare. This includes protecting
ecosystems, such as plants and animals, from harm, as well as protecting against
decreased visibility and damage to crops, vegetation, and buildings.

US-EPA has set National Air Quality Standards (NAAQS) for six principal air
pollutants: nitrogen oxides (expressed as NO
2
), ozone, sulfur dioxide, PM, carbon
monoxide (CO), and lead (Pb). Four of these pollutants (CO, Pb, NO, and SO
2
) are
emitted directly from a variety of sources. Ozone is not directly emitted, but is
formed when nitrogen oxides (NO
X
) and VOCs react in the presence of sunlight.
PM is mostly directly emitted, but PM2.5 particles can also be added as secondary
pollutants (sulfates, nitrates, and organic particles).

The US-EPA has a large network of monitoring stations measuring the levels of
these pollutants in the air (ambient concentrations). A comprehensive annual
report and air trends
20
publications are also distributed by the US-EPA.
Furthermore, the US-EPA provides estimates and trends of emission rates for
various source types
21
.

The United States Clean Air Act
22
provides the principal framework for national,
state, tribal, and local efforts to protect air quality. Improvements in air quality are
the result of effective implementation of clean air laws and regulations, as well as
efficient industrial technologies. Under the Clean Air Act, the US-EPA has a
number of responsibilities, including the following:
Conducting periodic reviews of the NAAQS for the six principal pollutants
that are considered harmful to public health and the environment.

Ensuring that these air quality standards are met (in cooperation with the
state, tribal, and local governments) through national standards and
strategies to control air pollutant emissions from vehicles, factories, and
other sources.

Reducing emissions of SO
2
and NO
X
that cause acid rain.

Reducing air pollutants such as PM, SO
X
, and NO
X
, which can reduce
visibility across large regional areas, including many of the nations parks
and wilderness areas.


19
http://www.gsf.de/eurotrac
20
http://www.epa.gov/air/airtrends/reports.html
21
http://www.epa.gov/air/airtrends/aqtrnd03/
22
http://www.epa.gov/oar/caa/contents.html
8 Ambient Air Pollution 1 An Introduction to Air Pollution 8




Ensuring that sources of toxic air pollutants that may cause cancer and other
adverse human health and environmental effects are well controlled and
that the risks to public health and the environment are substantially reduced.

Limiting the use of chemicals that damage the stratospheric ozone layer in
order to prevent increased levels of harmful UV radiation.

More information can be found at http://www.epa.gov/oar/caa/contents.html.



4 Classifications of Air Pollutants and Their Trends

4.1 Criteria Pollutants

As listed above, there are 6 principal, or criteria pollutants regulated by the
US-EPA and most countries in the world:
Total suspended particulate matter (TSP), with additional subcategories of
particles smaller then 10 m in diameter (PM
10
), and particles smaller than
2.5 m in diameter (PM
2.5
). PM can exist in solid or liquid form, and
includes smoke, dust, aerosols, metallic oxides, and pollen. Sources of PM
include combustion, factories, construction, demolition, agricultural
activities, motor vehicles, and wood burning. Inhalation of enough PM
over time increases the risk of chronic respiratory disease.


Sulfur dioxide (SO
2
). This compound is colorless, but has a suffocating,
pungent odor. The primary source of SO
2
is the combustion of
sulfur-containing fuels (e.g., oil and coal). Exposure to SO
2
can cause the
irritation of lung tissues and can damage health and materials.

Nitrogen oxides (NO and NO
2
). NO
2
is a reddish-brown gas with a sharp
odor. The primary source of this gas is vehicle traffic, and it plays a role in
the formation of tropospheric ozone. Large concentrations can reduce
visibility and increase the risk of acute and chronic respiratory disease.

Carbon monoxide (CO). This odorless, colorless gas is formed from the
incomplete combustion of fuels. Thus, the largest source of CO today is
motor vehicles. Inhalation of CO reduces the amount of oxygen in the
bloodstream, and high concentrations can lead to headaches, dizziness,
unconsciousness, and death.

Ozone (O
3
). Tropospheric (low-level) ozone is a secondary pollutant
formed when sunlight causes photochemical reactions involving NO
X
and
VOCs. Automobiles are the largest source of VOCs necessary for these
reactions. Ozone concentrations tend to peak in the afternoon, and can
cause eye irritation, aggravation of respiratory diseases, and damage to
plants and animals.
9 Ambient Air Pollution 1 An Introduction to Air Pollution 9




Lead (Pb). The largest source of Pb in the atmosphere has been from leaded
gasoline combustion, but with the gradual elimination worldwide of lead in
gasoline, air Pb levels have decreased considerably. Other airborne sources
include combustion of solid waste, coal, and oils, emissions from iron and
steel production and lead smelters, and tobacco smoke. Exposure to Pb can
affect the blood, kidneys, and nervous, immune, cardiovascular, and
reproductive systems.

Below is a graph showing the almost general decline in concentration of these
criteria pollutants in the United States (courtesy of US-EPA data from their
National Air Quality and Emissions Report, 1996 and 2003
23
):



The following graphs (see electronic book for full color versions) depicting similar
trends in UK air pollutants are from the National Environmental Technology
Center
24
(Smoke is soot emitted from burning coal, and is a type of Particulate
Matter).














23
http://www.epa.gov/air/airtrends/reports.html
24
http://www.airquality.co.uk/archive/reports/cat05/0408161000_Defra_AQ_Brochure_2004_s.pdf
10 Ambient Air Pollution 1 An Introduction to Air Pollution 10









In order to obtain more comprehensive and representative data on ozone air
pollution, the US-EPA air monitoring regulations now require US states to
establish networks of Photochemical Assessment Monitoring Stations (PAMS) in
areas where ozone air pollution is a serious problem. These stations provide
enhanced monitoring of ozone and its precursors (NO
X
and VOCs), as well as some
meteorological data. More information is listed at:
http://www.epa.gov/oar/oaqps/pams/general.html.
11 Ambient Air Pollution 1 An Introduction to Air Pollution 11




4.2 Toxic Pollutants

Hazardous air pollutants (HAPS)
25
, also called toxic air pollutants or air toxics, are
those pollutants that cause or may cause cancer or other serious health effects, such
as reproductive effects or birth defects. The US-EPA is required to control 188
hazardous air pollutants
26
. Examples of toxic air pollutants include benzene, which
is found in gasoline; perchlorethlyene, which is emitted from some dry cleaning
facilities; and methylene chloride, which is used as a solvent and paint stripper by a
number of industries. The following graph (which is figure 5.4 in the original
reference) of benzene concentrations is courtesy of US-EPA data from their
National Air Quality and Emissions Report, 2003
27
:



4.3 Radioactive Pollutants

Radioactivity
28
is an air pollutant that is both geogenic and anthropogenic.
Geogenic radioactivity results from the presence of radionuclides, which originate
either from radioactive minerals in the earths crust or from the interaction of
cosmic radiation with atmospheric gases. Anthropogenic radioactive emissions
originate from nuclear reactors, the atomic energy industry (mining and processing
of reactor fuel), nuclear weapon explosions, and plants that reprocess spent reactor
fuel. Since coal contains small quantities of uranium and thorium, these




25
http://www.epa.gov/ttn/atw/pollsour.html
26
http://www.epa.gov/ttn/atw/orig189.html
27
http://www.epa.gov/air/airtrends/aqtrnd03/
28
http://epa.gov/radtown/air.htm
12 Ambient Air Pollution 1 An Introduction to Air Pollution 12




radioactive elements can be emitted into the atmosphere from coal-fired power
plants and other sources
29
.

4.4 Indoor Pollutants
30


When a building is not properly ventilated, pollutants can accumulate and reach
concentrations greater than those typically found outside. This problem has
received media attention as Sick Building Syndrome. Environmental tobacco
smoke (ETS) is one of the main contributors to indoor pollution, as are CO, NO,
and SO
2
, which can be emitted from furnaces and stoves. Cleaning or remodeling a
house is an activity that can contribute to elevated concentrations of harmful
chemicals such as VOCs emitted from household cleaners, paint, and varnishes.
Also, when bacteria die, they release endotoxins into the air, which can cause
adverse health effects
31
. So ventilation is important when cooking, cleaning, and
disinfecting in a building. A geogenic source of indoor air pollution is radon
32
.

More information on indoor air pollution can be found at
http://www.epa.gov/iaq/pubs/hpguide.html



5 Emission Trends of Pollutants

The following graph (see electronic book for full color version) was created using
data from the US-EPA National Emissions Inventory (NEI) Emissions Trends Data,
1970-2002
33
. The graph illustrates the substantial decrease in emission rates
obtained in the US in the last decades, in spite of the dramatic increase of
population, traffic, and industrial activities.





















29
http://www.epa.gov/radtown/coal-plant.htm
30
http://www.epa.gov/iaq/
31
http://www.drlera.com/bacterial_diseases/bacterial_endotoxins.htm
32
http://www.epa.gov/radon/
33
http://www.epa.gov/ttn/chief/trends/
13 Ambient Air Pollution 1 An Introduction to Air Pollution 13






The following graph (Figure 5-3 in the original publication) is courtesy of US-EPA
data from their National Air Quality and Emissions Report, 2003
34
). The graph
illustrates an encouraging trend of reduction of toxic ambient concentrations.



Finally, the following two graphs depict emission trends in large developing
nations (China and India) and were created from data collected by the World


34
http://www.epa.gov/air/airtrends/aqtrnd03/
14 Ambient Air Pollution 1 An Introduction to Air Pollution 14




Resources Institute.
35
The graphs illustrate a typical behavior of large emerging
economies.













35
http://earthtrends.wri.org
15 Ambient Air Pollution 1 An Introduction to Air Pollution 15